Quinazoline derivative vat dyestuffs



Patented Jan. 22, 1952 QUINAZOLINE DERIVATIVE VAT DYE STUFFS Paul Sutter, Binningen, and Walter Kern, Sissach, Switzerland, assignors to. Ciba Limited,

Basel, Switzerland, a Swiss firm i No Drawing. Application September 11, 1950,

Serial No. 184,343. In Switzerland September 15Claims, (01. 260261) This invention relates to the manufacture of new vat dyestuffs. y 1

It is known that among the q-uinazoline derivativesthere are some which are valuable intermediate products for the. manufacture of vat dyestuffs (see French Patents Nos. 822,194'and 822,- 428) These 'quinazolines have however hitherto mostly been produced by alkaline ring c1osure of 2-aroylamino-anthraquinone-3-carboxylic .acid amides, according to the scheme r 0 M y 0 a /NH--O OR N o O-NHn in which R indicates an aromatic radical, especially a benzene radical. Thereupon the OH group in the quinazoline radical-was replaced by chlorine. A further examination of this process has shown that ring closure only takes place when the radical R is aromatic.

The subject of U. S. patent application Serial No. 756,808, filed June 24, 1947 (now Patent N0. 2,530,025) is a simplified process for the manufacture of quinazoline derivativeaas therein defined, which process consists in that acylaminoanthraquinone-ortho-nitriles are heated with phosphorous pentachloride.

The present invention is in part based upon the observation that a valuable quinazoline derivative can be produced when 3-cyano-2-cinnamoylamino-anthraquinone is subjected to the quinazoline ring closure with phosphorus pentachloride.

,The compound serving as starting material in this feature of the present invention can be,.ob-' tained in a simple manner by acylation of 3-cyano-2-aminoanthraquinone by means of cinnamic acid chloride, The ring. closure to the corresponding quinazoline derivatives, as above stated, takes place with the aid of phosphorous pentachloride and it can be carried out, advantageously in an indiiierentagent such as nitrobenzene, at elevated temperature, for example between 150? C. and the boiling point of the nitrobenzene. In this manner the quinazoline derivative is obtained of the formula The success of this process is surprising since, according to the process initially mentioned herein, by means of alkaline ring closure from 2-cinnamoylamino anthraquinone 3 carboxylic acid amide the corresponding 4- hydroxy quinazoline derivative cannot be obtained.

According to a further feature of the present invention valuable new vat dyestuffs are obtained by reacting the quinazoline obtained according to the above directions, which is substituted in 4-position oi the quinazolineradical by chlorine and in 2-position by the grouping -CH:CH- phenyl, with 4-aminoanthraquinone-2 :'l+ (N) benzene acridones. In this manner dyestuffs are obtained of valuable green color shades and good fastness properties, such a'sarev not" easily obtainable with other components in the-same color shades with similar rasmess' properties. The 4- aminoanthraquinone-Z 1 (N) -benzene acridones to be employed can, if "desired, also contain fur ther substituents, for example halogen atoms; such as chlorine, bromine, or fluorine, for example in one or both of thepositions, (i and .7015 the anthraquinone .radical, or especially in the. Bz-nucleus, for example a chlorine atom in para or meta-position to the nitrogen atom of the acridone ring. As examples may be mentioned 5'-chloro' and 6'-ch1oro-4-amino anthraduinone- 2:1(N)-1':2'-(N)'-benzene acridone and also 4- amino 6':'7 dichloranthraquinone 2:1(N)- 1:2'(N)-benzene acridone. The last mentioned amine component is new and can be produced from 1 amino 4 bromo 6:7 dichloranthraquinone-Z-sulfonic acid by methods known per se.

The reaction of the quinazoline with the aminoanthraquinone benzacridone is advantageously carried out in such a manner that per mol 0! the quinazoline one mol of the amine is em;

ployed. The reaction can be carried out for,

example in high boiling solvents such as nitro-t artificial silk and also staple fiber from regenerated cellulose. They can also be converted according to known processes into salts ofzthe leuco-sulfuric acid esters and similar compounds and can be employed according to the methods The good customary for this class of'dyestuffs. fastness properties of the dyestuffs obtained, especially their good resistance to thecombined chlorine bucking, are surprisingin consideration.

of the presence of the unsaturated araliphatic radical The following examples illustrate the invention, the parts and percentages being by weight unless otherwise stated and the'relation'between parts by weight'andparts by volume being the same as that between the kilogram and the liter:

Emtmplel J 3.8 parts of 2-cinnamoylamino-3-cyananthraquinone of the formula 4.2; parts of the product obtained according to Example 1 of the formula are heated to boiling for /4 hour together with 3.2 parts of 4-aminoanthraquinone-2:1(N) benzeneacridone in l05'parts of phenol. After the addition of 105 parts of pyridine the-whole is cooled" to about 60 C., filtered and'the residue washed'withbenzene and dried. The condensation' product can be purifiedby fractional crys-' 4 tallization from sulfuric acid. It corresponds to the formula.

and dissolves in concentrated sulfuric acid with a brown color and dyes cotton from a violet brown vat, in fast bottle green shades.

Example 3 1.5 parts of the chloroquinazoline obtained according to Example 1 are heated for -10 minutes to boiling together. with 1.4 parts of 5'-'chloro-4 aminoanthraquinone 2:1(N) 1.:2' (N) benzene acridone'in 20 parts of phenol. Thereupon 20 parts of pyridine are added, the whole allowed to cool to about 50 C. and filteredwith suction and the residue washed with alcohol and dried. The crude product thus obtained can be purified in the following manner: It is dissolved in about 50 times the quantity of sulfuric acid of-"9B per cent. strength and somuch 50 per cent; sulfuric acid added that the final concentration amounts to 76 per cent., whereupon the. brown sulfate which recrystallizes out is filtered with suction, decomposed with water, washed and dried.

The dyestuff thus produced corresponds to the formula V and dyes cotton from a violet-brown vat in yellow-green shades. 1

By taking in this example instead of 5'-chloro- 4aminoanthraquinone-2 l (N) .-1 :2 (N) '-benzene acridone the 6 chloro-4-aminoanthraquinone- 2:1(N)-1':2' (Ni-benzene acridone a" similar dyestuff is obtained.

Example 4 1.5 parts ofthechloroquinazoline obtained according to Example 1 are heated to boiling for hour with 1.4 parts of 4-amino-6z7-dichloroanthraquinone 2:1(N) -1' :2 (N) -benzene acridone in 20 parts of phenol. 20 parts of pyridine are added and the whole cooled to about 50 C. and filtered with suction and the residue washed with alcohol. The crude product can be purified in a similar manner to that described in Example 3. A product is thus obtained which corresponds to the formula i J... I ll o o o and dyes cotton from a brown vat in yellow-green shades.

The 6 7 2:1(N)-1':2'(N)-benzene acridone employed in this example is new and can be produced for example as follows:

29.2 parts of powdered. 1-amino-61'7-dichloranthraquinone in 300 parts of trichlorobenzene, after addition of 15 parts of chlorsulfonic acid, are gradually heated to 200 C. and maintained for two hours at this temperature. After cooling 500 parts of water are added and then ammonia to the production of an alkaline reaction, whereupon the trichlorobenzene is distilled off with steam. The solution is filtered hot and the ammonium salt of the 1-amino-6z'l-dichloranthraquinone-2-sulfonic acid salted out by addition of ammonium sulfate. After filtration with suction, washing and drying, it is obtained in small red needles.

33 parts of finely powdered ammonium salt are suspended in 900 parts of water and parts of concentrated sulfuric acid. Thereupon 15.5 parts of bromine are added gradually at 0 to 5 C. and the whole is stirred for a prolonged period at this temperature and then diluted with 4000 parts of water, ammonia added to the production of an alkaline reaction and then the whole heated to boiling and filtered hot with suction. From the fi1trate,'by addition of ammonium sulfate, the ammonium salt of the 1-amino-4-bromo-6z7-dichloranthraquinone 2 sulfonic acid is precipitated in the form of red needles.

4'? parts of the ammonium salt thus produced are mixed with 5 parts of cuprous chloride and 2 parts of copper powder and this mixture gradually introduced into a solution of 100 parts of sodium acetate, 8 parts of sodium carbonate and 20 parts of anthranilic acid in 2000 parts of water. After heating for 2 hours to 80 C., the blue solution is filtered with suction and the residue washed with hot water and the filtrate acidified and the precipitated blue product filtered with suction, washed and dried.

dichloro 4 aminoanthraquinone- 39 parts of the compound produced as above of the formula O NH:

are dissolved in 1500 parts of water and 9 parts of sodium carbonate. A mixture of 16.2 parts of sodium hydrosulfite with 13.5 parts of sodium carbonate is gradually added. The desulfonated product precipitates gradually. After some time it is filtered with suction, thoroughly washed and dried.

33 parts of the blue powder produced :as above are introduced into 230 parts of chlorsulfonic acid and stirred for 4 hours at 2025 C. The whole is diluted first with sulfuric acid and then with water with the production of a sulfuric acid of 65 per cent. strength, the temperature being allowed to rise to C. After cooling and filtering with suction the product is washed with water and dried. The 4-amino-6z'l-dichloranthraquinone- 2 1(N) -1' :2(N) -benzene acridone thus produced of the formula l) NH2 is a deep blue powder.

Example 5 1 part of the dyestuif obtained according to Example 2 is vatted at 50-60 C. in 100 parts of water by addition of 2 parts of sodium hydrosulfite and 4 parts by volume of caustic soda solution of 36 B. The above stock vat is added to a dyebath which contains in 3000 parts of water 8 parts by volume of caustic soda solution of 36 B. and 3 parts of sodium hydrosulfite. 100 parts of cotton are entered at 40 C. into the dyebath thus obtained, 30 parts of sodium chloride are added after A hour and dyeing is carried out for one hour with increase of the temperature to 50 C. 'I'hereupon the cotton is squeezed out, oxidized in the air, rinsed, acidified, again rinsed and soaped at the boil. It becomes dyed in fast bottle green shades.

What we claim is:

1. A vat dyestuff of the general formula wherein R. stands for the radical of an anthraquinone-2:l(N) -benzene acridone attached to sum-520 7 the J -NH group in set-position 4'0! *the anthraquinone radical.

2. The vat dyestufimf the formula 3. "The -va1; :dyestuff if :the :iiarmula 8 4. ,The vat dyestufi of the formula 5. A process for the manufacture "of vat dyestuffs which comprises heating the ,quinazoline derivative of the formula with a 4-amino-anthraquinone-2 1 (N) -benzene acridone.

PAUL SUTT-ER. -WAL'I'ER KERN.

. No references cited. 

1. A VAT DYESTUFF OF THE GENERAL FORMULA 